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EP0003237B1 - Use of an amorphous alloy of silicon and germanium as against gallium-arsenide laser radiation sensitive photoconductor - Google Patents

Use of an amorphous alloy of silicon and germanium as against gallium-arsenide laser radiation sensitive photoconductor Download PDF

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Publication number
EP0003237B1
EP0003237B1 EP78101834A EP78101834A EP0003237B1 EP 0003237 B1 EP0003237 B1 EP 0003237B1 EP 78101834 A EP78101834 A EP 78101834A EP 78101834 A EP78101834 A EP 78101834A EP 0003237 B1 EP0003237 B1 EP 0003237B1
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EP
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Prior art keywords
germanium
photoconductor
silicon
amorphous
laser radiation
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EP78101834A
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German (de)
French (fr)
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EP0003237A1 (en
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Jacques Paul Chevallier
Charles Richard Guarnieri
Aare Onton
Harold Wieder
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International Business Machines Corp
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International Business Machines Corp
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10FINORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00Manufacture or treatment of devices covered by this subclass
    • H10F71/10Manufacture or treatment of devices covered by this subclass the devices comprising amorphous semiconductor material
    • H10F71/103Manufacture or treatment of devices covered by this subclass the devices comprising amorphous semiconductor material including only Group IV materials
    • H10F71/1035Manufacture or treatment of devices covered by this subclass the devices comprising amorphous semiconductor material including only Group IV materials having multiple Group IV elements, e.g. SiGe or SiC
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10FINORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F30/00Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors
    • H10F30/10Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices being sensitive to infrared radiation, visible or ultraviolet radiation, and having no potential barriers, e.g. photoresistors
    • H10F30/15Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices being sensitive to infrared radiation, visible or ultraviolet radiation, and having no potential barriers, e.g. photoresistors comprising amorphous semiconductors
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10FINORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00Constructional details of devices covered by this subclass
    • H10F77/10Semiconductor bodies
    • H10F77/16Material structures, e.g. crystalline structures, film structures or crystal plane orientations
    • H10F77/162Non-monocrystalline materials, e.g. semiconductor particles embedded in insulating materials
    • H10F77/166Amorphous semiconductors
    • H10F77/1662Amorphous semiconductors including only Group IV materials
    • H10F77/1665Amorphous semiconductors including only Group IV materials including Group IV-IV materials, e.g. SiGe or SiC
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/548Amorphous silicon PV cells
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to the use of an amorphous alloy of silicon and germanium containing hydrogen as a photoconductor sensitive to gallium arsenide laser radiation.
  • Photoconductor sensitive to infrared radiation with a high dark resistance and fast response times are interesting for applications in devices which are activated by radiation at high speed.
  • photoconductors are desired which are sensitive to radiation from a gallium arsenide laser whose maximum emitted energy is approximately 1.5 eV.
  • amorphous silicon and amorphous germanium in a glow discharge process were described by Chittick in Journal of Non-crystalline Solids, Volume 3, (1970), pages 255 to 270.
  • Chittick stated that amorphous silicon containing hydrogen, which was caused by the glow discharge manufacturing process, was a very good photoconductor in the spectral region of about 2 eV. However, the photoconductivity decreased significantly below 2 eV and was relatively weak at 1.5 eV, the wavelength of the gallium arsenide laser. Chittick also stated that amorphous germanium made by the same process and containing hydrogen had no measurable photoconductivity and low dark resistance.
  • Crystalline silicon-germanium alloys have been produced by a method which is described by Braunstein in Physical Review, volume 130 (1963), page 869. These alloys also do not show any measurable photoconductivity.
  • the object of the invention is the use of the amorphous alloys described above as a photoconductor which has improved radiation sensitivity in the infrared spectral range.
  • the photoconductor is said to be sensitive to radiation from a gallium arsenide laser at 1.5 eV. In addition, this photoconductor should have a short response time and a high dark resistance.
  • a composition of a preferred embodiment is amorphous Si x Ge 1 _ X Hy, in which x covers a range from 0.78 to 0.93 and y covers a range from 14 to 22 atomic percent.
  • This material is a very good photoconductor at 1.5 eV and has a high dark resistance of about 10 8 ohmxcm and a fast response time, ie a mobility of 5 ⁇ 10 -2 cm2 / Vs.
  • an improved photoconductor for devices addressable with gallium arsenide laser radiation which is sensitive to radiation at approximately 1.5 eV, consists of amorphous material containing silicon, hydrogen and a material from the group of germanium, tin and lead .
  • the amorphous silicon alloy contains germanium.
  • a preferred concentration range for germanium is given when x is between 0.78 and 0.93.
  • the amorphous alloys can be produced by glow discharge or alternatively in a sputtering system, the corresponding elements being contained in a carrier gas made of hydrogen. Both methods are known per se.
  • a Amorphous Si-GeH alloy is produced by simultaneously filling silane and german into the reaction chamber of the glow discharge process.
  • a film with a layer thickness of 1 to 3 ⁇ m from amorphous Si x Ge 1-x H y in which x is 0.93 and y is between 14 and 20 atomic percent was obtained by high-frequency glow discharge decomposition of gaseous silane and German .
  • the substrate temperature was constant and was around 250 ° C. Hydrogen is present in this glow discharge process.
  • the photoconductivity, which shows the shift of the absorption edge further into the infrared spectral range, can be seen from FIG. 1, in which it is compared with an amorphous silicon alloy in which a similar amount of hydrogen is incorporated.

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Description

Die Erfindung betrifft die Verwendung einer amorphen Legierung aus Silicium und Germanium mit einem Gehalt an Wasserstoff als gegen Galliumarsenid-Laserstrahlung empfindlichen Photoleiter.The invention relates to the use of an amorphous alloy of silicon and germanium containing hydrogen as a photoconductor sensitive to gallium arsenide laser radiation.

Gegen Infrarotstrahlung empfindliche Photoleiter. mit einem hohen Dunkelwiderstand und schnellen Ansprechzeiten sind interessant für Anwendungen irf Vorrichtungen, die mit hoher Geschwindigkeit durch Strahlung activiert werden. Insbesondere sind Photoleiter erwünscht, welche gegen Strahlung eines Galliumarsenid-Lasers, dessen Maximum der emittierten Energie bei etwa 1,5 eV liegt, empfindlich sind.Photoconductor sensitive to infrared radiation. with a high dark resistance and fast response times are interesting for applications in devices which are activated by radiation at high speed. In particular, photoconductors are desired which are sensitive to radiation from a gallium arsenide laser whose maximum emitted energy is approximately 1.5 eV.

Die Herstellung amorphen Siliciums und amorphen Germaniums in einem Glimmentladungsverfahren wurde von Chittick in Journal of Non-crystalline Solids, Band 3, (1970), Seiten 255 bis 270 beschrieben. Chittick gab an, daß amorphes Silicium mit einem Gehalt an Wasserstoff, der durch das Herstellungsverfahren der Glimmentladung bedingt war, ein sehr guter Photoleiter in dem Spektralgebiet von etwa 2 eV war. Die Photoleitfähigkeit sank jedoch im beträchtlichem Maße ab bei Werten unterhalb 2 eV und war bei 1,5 eV, der Wellenlänge des Galliumarsenid-Lasers verhältnismäßig schwach. Chittick gab auch an, daß amorphes Germanium, welches nach dem gleichen Verfahren hergestellt wurde und Wasserstoff enthielt, keine meßbare Photoleitfähigkeit und einen niedrigen Dunkelwiderstand aufwies.The production of amorphous silicon and amorphous germanium in a glow discharge process was described by Chittick in Journal of Non-crystalline Solids, Volume 3, (1970), pages 255 to 270. Chittick stated that amorphous silicon containing hydrogen, which was caused by the glow discharge manufacturing process, was a very good photoconductor in the spectral region of about 2 eV. However, the photoconductivity decreased significantly below 2 eV and was relatively weak at 1.5 eV, the wavelength of the gallium arsenide laser. Chittick also stated that amorphous germanium made by the same process and containing hydrogen had no measurable photoconductivity and low dark resistance.

Kristalline Silicium-Germaniumlegierungen sind nach einem Verfahren hergestellt worden, das von Braunstein in Physical Review, Band 130 (1963), Seite 869 beschrieben ist, Auch diese Legierungen zeigen keine meßbare Photoleitfähigkeit.Crystalline silicon-germanium alloys have been produced by a method which is described by Braunstein in Physical Review, volume 130 (1963), page 869. These alloys also do not show any measurable photoconductivity.

Beaglehole gab in Journal of Non-Crystalline Solids, Band 4 (1970), Seite 272 an, daß amorphe Silicium-Germaniumlegierungen, welche durch gemeinsame Verdampfung hergestellt worden waren, keine beobachtbare Photoleitfähigkeit aufwiesen. Die amorphen Silicium-Germaniumlegierungen, die nach diesem Verfahren hergestellt worden waren, enthielten auf Grund ihrer Herstellungsmethode keinen Wasserstoff.Beaglehole in Journal of Non-Crystalline Solids, Volume 4 (1970), page 272 stated that amorphous silicon-germanium alloys which had been produced by co-evaporation had no observable photoconductivity. The amorphous silicon-germanium alloys that were produced by this process contained no hydrogen due to their manufacturing method.

J. Chevallier et al beschreiben in Solid State Comm., Vol. 24, Seiten 867 bis 869, 1977 die optischen Eigenschaften von amorphen SixGe1-x(H)-Legierungen. Sie geben für die Abhängigkeit der optischen Absorptionskante von der Legierungszusammensetzung eine lineare Beziehung E ―0,95+0,70x(eV) an. Die Photoleitfähigkeit der Legierungen ist in dieser Veröffentlichung nicht beschrieben.J. Chevallier et al in Solid State Comm., Vol. 24, pages 867 to 869, 1977 describe the optical properties of amorphous Si x Ge 1-x (H) alloys. They give a linear relationship E ―0.95 + 0.70x (eV) for the dependence of the optical absorption edge on the alloy composition. The photoconductivity of the alloys is not described in this publication.

Aufgabe der Erfindung ist die Verwendung der zuvor beschriebenen- amorphen Legierungen als Photoleiter, der eine verbesserte Strahlungsempfindlichkeit im Infrarotspektralbereich aufweist.The object of the invention is the use of the amorphous alloys described above as a photoconductor which has improved radiation sensitivity in the infrared spectral range.

Der Photoleiter soll gegen Strahlung eines Galliumarsenid-Lasers bei 1,5 eV empfindlich sein. Außerdem soll dieser Photoleiter eine kurze Ansprechzeit und einen hohen Dunkelwiderstand aufweisen.The photoconductor is said to be sensitive to radiation from a gallium arsenide laser at 1.5 eV. In addition, this photoconductor should have a short response time and a high dark resistance.

Die Aufgabe der Erfindung wird gelöst durch einen Photoleiter, dessen Zusammensetzung in den Patentansprüchen angegeben ist.The object of the invention is achieved by a photoconductor, the composition of which is specified in the patent claims.

Der Photoleiter besteht aus einer amorphen SixA1-yHy-Legierung, in der A Ge, Sn oder Pb ist und x=0,50 bis 0,99 und y=1 bis 50 Atomprozent bedeuten. Eine Zusammensetzung eines bevorzugten Ausführungsbeispiels ist amorphes SixGe1_XHy, in dem x ein Bereich von 0,78 bis 0,93 und y einen Bereich von 14 bis 22 Atomprozent abdeckt. Dieses Material ist bei 1,5 eV ein sehr guter Photoleiter und weist einen hohen Dunkelwiderstand von etwa 108 Ohmxcm und eine schnelle Ansprechzeit, d.h. eine Beweglichkeit von 5×10-2 cm2/Vs auf.The photoconductor consists of an amorphous Si x A 1-y H y alloy, in which A is Ge, Sn or Pb and x = 0.50 to 0.99 and y = 1 to 50 atomic percent. A composition of a preferred embodiment is amorphous Si x Ge 1 _ X Hy, in which x covers a range from 0.78 to 0.93 and y covers a range from 14 to 22 atomic percent. This material is a very good photoconductor at 1.5 eV and has a high dark resistance of about 10 8 ohmxcm and a fast response time, ie a mobility of 5 × 10 -2 cm2 / Vs.

Die Erfindung wird anhand von Fig. 1 und der nachfolgenden detaillierten Beschreibung näher erläutert.The invention is explained in more detail with reference to FIG. 1 and the following detailed description.

Fig. 1 zeigt die Abhängigkeit der Photoleitfähigkeit in der Umgebung der Absorptionskante von der einfallenden Wellenlänge für drei Zusammensetzungen des Photoleiters, verglichen mit amorphem Silicium mit einem vergleichbaren Gehalt an Wasserstoff.1 shows the dependence of the photoconductivity in the vicinity of the absorption edge on the incident wavelength for three compositions of the photoconductor, compared to amorphous silicon with a comparable content of hydrogen.

Gemäß der vorliegenden Erfindung besteht ein verbesserter Photoleiter für mit Galliumarsenid-Laserstrahlung adressierbare Geräte, der gegenüber Strahlung bei etwa 1,5 eV empfindlich ist, aus amorphem Material mit einem Gehalt an Silicium, Wasserstoff und einem Material aus der Gruppe von Germanium, Zinn und Blei. Die allgemeine Formel dieser amorphen Legierung ist SixA1-xHy, in der A Ge, Sn oder Pb ist und x=0,50 bis 0,99 und y=1 bis 50 Atomprozent bedeuten.According to the present invention, an improved photoconductor for devices addressable with gallium arsenide laser radiation, which is sensitive to radiation at approximately 1.5 eV, consists of amorphous material containing silicon, hydrogen and a material from the group of germanium, tin and lead . The general formula of this amorphous alloy is Si x A 1-x H y , in which A is Ge, Sn or Pb and x = 0.50 to 0.99 and y = 1 to 50 atomic percent.

In einem bevorzugten Ausführungsbeispiel enthält die amorphe Siliciumlegierung Germanium. Ein bevorzugter Konzentrationsbereich für Germanium ist gegeben, wenn x zwischen 0,78 und 0,93 liegt. Durch Zugabe von Germanium, Zinn oder Blei, beispeilsweise von Germanium, wird die Absorptionskante des amorphen Siliciums weiter in den infraroten Spektralbereich verschoben, ohne daß die Ansprechzeit und der Dunkelwiderstand, welche mit amorphem Silicium allein erhalten werden, nachteilig beeinflußt werden, so daß eine Empfindlichkeit auf Galliumarsenid-Laserstrahlung bei 1,5 eV erhalten wird.In a preferred embodiment, the amorphous silicon alloy contains germanium. A preferred concentration range for germanium is given when x is between 0.78 and 0.93. By adding germanium, tin or lead, for example germanium, the absorption edge of the amorphous silicon is shifted further into the infrared spectral range without the response time and the dark resistance which are obtained with amorphous silicon alone being adversely affected, so that sensitivity is obtained on gallium arsenide laser radiation at 1.5 eV.

Die amorphen Legierungen können durch Glimmentladung oder alternativ in einem Kathodenzerstäubungssystem hergestellt werden, wobei die entsprechenden Elemente in einem Trägergas aus Wasserstoff enthalten sind. Beide Verfahren sind an sich bekannt. Eine amorphe Legierung aus Si-GeH wird hergestellt, indem gleichzeitig Silan und German in die Reaktionskammer des Glimmentladungsverfahrens eingefüllt werden.The amorphous alloys can be produced by glow discharge or alternatively in a sputtering system, the corresponding elements being contained in a carrier gas made of hydrogen. Both methods are known per se. A Amorphous Si-GeH alloy is produced by simultaneously filling silane and german into the reaction chamber of the glow discharge process.

Beispiel 1example 1

Ein Film mit einer Schichtdicke von 1 bis 3 ,um aus amorphem SixGe1-xHy, in dem x 0,93 ist und y zwischen 14 und 20 Atomprozent liegt, wurde durch eine Hochfrequenz-Glimmentladungszersetzung von gasförmigem Silan und German erhalten. Die gemischten Gase wurden bei einem Druck von 41,23 Pa umgesetzt, die Fließgeschwindigkeit betrug 0,6 (Scm3/s) (S=Standard) une eine Hochfrequenzenergie von etwa 24 Watt wurde angewendet. Die Substrattemperatur war konstant und lag bei etwa 250°C. In diesem Glimmentladungsverfahren ist Wasserstoff anwesend. Die Photoleitfähigkeit, die die Verschiebung der Absorptionskante weiter in den infraroten Spektralbereich zeigt, ist aus Fig. 1 ersichtlich, in der sie mit einer amorphen Siliciumlegierung verglichen wird, in der eine ähnliche Menge Wasserstoff eingebaut ist.A film with a layer thickness of 1 to 3 µm from amorphous Si x Ge 1-x H y in which x is 0.93 and y is between 14 and 20 atomic percent was obtained by high-frequency glow discharge decomposition of gaseous silane and German . The mixed gases were reacted at a pressure of 41.23 Pa, the flow rate was 0.6 (Scm 3 / s) (S = standard) and a radio frequency energy of about 24 watts was used. The substrate temperature was constant and was around 250 ° C. Hydrogen is present in this glow discharge process. The photoconductivity, which shows the shift of the absorption edge further into the infrared spectral range, can be seen from FIG. 1, in which it is compared with an amorphous silicon alloy in which a similar amount of hydrogen is incorporated.

Beispiele 2 und 3Examples 2 and 3

Filme mit einem Germaniumgehalt, bei denen x in der Formel 0,78 und 0,54 bedeutet, wurden nach dem in Beispiel 1 angegebenen Verfahren hergestellt. Die Photoleitfähigkeit dieser beiden Materialien ist ebenfalls in Fig. 1 eingetragen.Films with a germanium content, in which x in the formula means 0.78 and 0.54, were produced by the method given in Example 1. The photoconductivity of these two materials is also shown in Fig. 1.

Wie in. Fig. 1 gezeigt ist, zeigen alle drei Legierungen der Beispiele 1, 2 und 3 eine Verschiebung der Absorptionskante weiter in den infraroten Spektralbereich. Diese wird erhalten, ohne daß der Dunkelwiderstand oder die Ansprechzeit des Materials nachteilig beeinflußt werden. Die drei angegebenen Legierungen weisen eine Empfindlichkeit gegen Galliumarsenid-Laserstrahlung bei 1,5 eV auf, die wesentlich größer ist als die eines amorphen Siliciums. das nur Wasserstoff enthält.As shown in FIG. 1, all three alloys of Examples 1, 2 and 3 show a shift of the absorption edge further into the infrared spectral range. This is obtained without adversely affecting the dark resistance or the response time of the material. The three alloys indicated have a sensitivity to gallium arsenide laser radiation at 1.5 eV, which is significantly greater than that of an amorphous silicon. that only contains hydrogen.

Claims (3)

1. Use of an amorphous alloy of the general formula SixA1-xHy, where A is Ge, Sn or Pb, and where x is 0.50 to 0.99, and where y is 1 to 50 atomic percent, as a photoconductor sensitive to illumination from a gallium arsenide laser.
2. Use of an alloy as claimed in claim 1, where A is germanium, as photoconductor.
3. Use of an alloy as claimed in claim 1, where x equals 0.78 to 0.93, and y equals 14 to 20 atomic percent, as a photoconductor.
EP78101834A 1978-01-13 1978-12-23 Use of an amorphous alloy of silicon and germanium as against gallium-arsenide laser radiation sensitive photoconductor Expired EP0003237B1 (en)

Applications Claiming Priority (2)

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US869194 1978-01-13
US05/869,194 US4147667A (en) 1978-01-13 1978-01-13 Photoconductor for GaAs laser addressed devices

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EP0003237A1 EP0003237A1 (en) 1979-08-08
EP0003237B1 true EP0003237B1 (en) 1983-05-18

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EP (1) EP0003237B1 (en)
JP (1) JPS5498588A (en)
AT (1) AT371949B (en)
CA (1) CA1111536A (en)
DE (1) DE2862265D1 (en)
IT (1) IT1160377B (en)

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AT371949B (en) 1983-08-10
JPS5498588A (en) 1979-08-03
IT1160377B (en) 1987-03-11
JPS5522950B2 (en) 1980-06-19
ATA934578A (en) 1982-12-15
CA1111536A (en) 1981-10-27
IT7831082A0 (en) 1978-12-21
EP0003237A1 (en) 1979-08-08
DE2862265D1 (en) 1983-07-07
US4147667A (en) 1979-04-03

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